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By N. S. Dalal, Xianglin Shi

"Electron spin resonance (ESR) measurements provide direct evidence for the involvement of Cr(V) in the reduction of Cr(VI)· by NAD(P)H. Addition of hydrogen peroxide (H2 O 2) to NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) signal and generates hydroxyl (·OH) radicals (as detected via spin trapping), suggesting that Cr(V) reacts with H2O 2 to generate the ·OH radicals. Reaction between H2O 2 and a Cr(V)·glutathione complex, and between H2O 2 and several Cr(V)-carboxylato complexes also produces ·OH radicals. These results suggest that Cr(V) complexes catalyze the generation of ·OH radicals from H2O 2, and that ·OH radicals might play a significant role in the mechanism of Cr(VI) cytotoxicity. KEY WORDS: ESR. spin trapping, Cr(VI) reduction, Cr(V), hydrogen peroxide, free radicals.INTRODUCTIONThis communication reports an ESR spin trapping detection of hydroxyl ( OH) radicals.in reactions between some Cr(V) complexes containing biologically important ligands and hydrogen peroxide (H2O 2 ). This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step in the mechanism of Cr(VI) toxicity, the reaction· mechanism is not yet clear. 1 Mutagencity has been well documented for Cr(VI) via various bacterial assays, while Cr(III) has been shown not to be mutagenic.2 • 3 Since it has been reported that compounds containing Cr(VI) do not react with isolated DNA,4 the reduction of Cr(VI) by other cellular constituents has been thought to be important in the mechanism of Cr(VI) induced DNA alteration.1·4 • 5 For cellular systems earlier studies include those on the reduction of C~(VI) by microsomes,6-8 rat liver DT-diaphorase,9 and aldehyde oxidase. 10 Regarding the reduction mechanism, Jennette used ESR spectroscopy to show that a long-lived Cr(V) complex is formed as an intermediate in the microsomal reduction of Cr(VI) in the presence of NADPH.8 She postulated that Cr(V) is the ""ultimate"" carcinogenic form of chromium compounds. This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions.11 - 19 More recently, however, it has been suggested that oxygen-derived radicals generated during the Cr(VI) reduction are the species responsible for the DNA alteration.20.2• To the best of our knowledge, however, no information is available on the generation of such radicals in the reduction of Cr(VI) under biologically relevant conditions, except some preliminary results on the glutathionyl (GS·) radical formation in the reduction of Cr(VI) by glutathione (GSH). 11 - 19 We, therefore, undertook a systematic investigation of the reaction of Cr(VI) with NAD(P)H, GSH, ix-hydroxycarboxylic acids, and H2O 2 • NADPH was chosen as a model reductant because of its ubiquitous existence inside the cells, its critical role in the enzymatic Cr(VI) reduction,1·6-9 its representation of important cellular Cr(VI) reductants, and its ability to reduce other metal ions.22 GSH was chosen as another model Cr(VI) reductant because GSH also exists inside cells, it represents another important category of cellular Cr(VI) reductants, the thiols, and it also plays an important role in the Cr(VI) toxicity .1• 1 ""- 19.i3.i4 For further clarification, we also studied the reaction of Cr(VI) with several '1'.-hydroxycarboxylic acids in the presence of H2O 2 since these acids are definitively known to reduce Cr(VJ) to form stable, isolable Cr(V).25 .2 6 The results obtained indicate that Cr(V) complexes, produced in the reduction of Cr(VJ) by cellular reductants, react with H2 O 2 to generate ·OH radicals, which might be the initiators of primary events in Cr(VI) carcinogenicity."

Jan 1, 1990

By E. G. King

Thermodynamic calculations involving the oxides of tungsten and molybdenum have been hampered by lack of accurate entropies and high temperature heat contents. This paper presents work by the Federal Bureau of Mines on new low-temperature heat-capacity data leading to the evaluation of the 298.15° K. entropies of tungsten dioxide and tungsten trioxide, as well as high-temperature heat contents (above 298.15° K.) of molybdenum dioxide, molybdenum tri-oxide, tungsten dioxide, and tungsten trioxide. Included are heats of fusion of the two trioxides. The heats of formation at 298.15° K. of these four oxides are tabulated as measured by Mah4 5/ of this laboratory. Included also are the 298.15° K. entropy of Mo02 measured by Kin 6/ of this laboratory, and that for Mo03 according to Kelley and King.7/ These basic data provide a consistent compilation from which to perform accurate thermodynamic calculations involving these compounds. No previous low-temperature- heat-capacity measurements have been reported for tungsten dioxide. Seltz, Dunkerley, and DeWitt8/ measured the low-temperature heat capacity of tungsten trioxide. The only previously-reported high-temperature heat-content measurements for any of the oxides were conducted by Cosgrove and Snyder,9/ who measured molybdenum trioxide to 1,300° K.

Jan 1, 1960

By F. E. Diebold

The wastewater-treatment system of the Anaconda Mining Co., at its Butte, MT., operation has been physically and chemically characterize modeled on a computer and investigated with respect to alternate systems for economic heavy metal recovery. The system involves lime addition to a mixture of acid underground copper sulfide mine water, acid effluent water from the iron induced precipitation of copper from acid leach solution and basic suspensions of solid effluent from a concentrator plant. Experimental chemical analysis and predictive computer calculations shows that the monosulfllte and disulfllte complexes of transition metals (Iron II being dominant) and alkaline earths are 40% of the total dissolved metal load of both acid streams. The suspended solids (30% by weight) in the basic concentrator slurries are dominated by quartz and pyrite and also contain kaolinite muscovite, biotite and undissolved lime. The mixture of these three streams result's in major reductions in concentrations of Al, Cu, Fe, Mg, Mn, Sir and Zn, and a pH >7 with calcium, sodium, potassium, and sulfate being the major dissolved ions. The treatment system has been simulated in the laboratory and accurately modeled on a computer. The computer program, an altered REDEQL-EPAK, is capable of accurately predicting the amount of lime required to reach a desired effluent water. Preliminary research has indicated the usefulness of electroprecipitation as a means of recovering the valuable metal load and providing an EPA acceptable effluent.

Jan 1, 1982

By R. T. Sorensen

Research and testing in a small scale equivalent of a commercial flota-tion plant was completed on four low-grade, iron-bearing materials from the western Mesabi range. Closed circuit-flotation of calcium-activated silica with fatty acid collector developed data for comparison with the batch process and highlighted problems not evident from previous bench testing. The four ore samples contained from 27 to 39 percent Fe and were equally represented by nonmagnetic taconite and semitaconite type materials. Iron concentrates containing 6.0 percent, or less, SiO2 were made 5, all four samples. Of the two material types, the semitaconite was the ore amenable to treatment, yielding iron recoveries of about 90 percent as cc pared with 70 to 80 percent for the other. Pilot plant tests showed that concentrate grade made in batch tests could be duplicated in the closed circuit and demonstrated that the amount of recoverable middling iron varied considerably between ore samples. The continuous tests also showed that water temperature strongly influenced results in the treatment of one ore but apparently was of indifferent consequence in another. Progress in thickening and filtration of flotation concentrates was made through introduction of tapioca flour to serve the dual role of iron mineral depressant and flocculant.

Jan 1, 1966

By R. R. Wells, G. M. Potter, R. Havens, W. W. Agey

"INTRODUCTION As part of the program of investigating possible domestic sources of manganese, ore-dressing studies were conducted at Salt Lake City, Utah, on five samples of manganese oxide ore obtained by mining engineers of the Bureau of Mines from the Havasu Lake District, California and Arizona.Two lots of radically different ores were procured from the Arizona Manganese claims 30 miles above Parker Dam, Mohave County, Ariz. One of the original 11 claims has been flooded by Havasu Lake, formed by Parker Dam. The claims are owned by R. H. Thompson, Parker Lumber Co., Parker, Ariz. The 2-ton lot of high-grade ""TA"" ore represented ore occurring as pyrolusite and psilomelane accompanied by a black calcite gangue in lenses along a series of fault planes in granite. A half-ton lot of low-grade ""TB"" ore was taken from a large lense of reddish iron-bearing material outcropping on another section of the property.A 2-ton lot of ore was taken from the Jones property, 8-1/2 miles southwest of Powell, Mohave County, Ariz. At the time of the investigation, the property was leased by J. H. Jones, of Oatman, Arix., from the owners, the Atchison, Topeka, & Santa Fe Railroad Co. The ore body was described as a re¬placement in a sandstone formation in a region that has been faulted extensively."

Dec 1, 1947

By Robert H. Peters

This report presents a literature review conducted by the U.S. Bureau of Mines. The review summarizes what has been learned from recent empirical studies of the relationship between mine safety and characteristics of miners, mine management, and mining companies. The review is based on literature published in the United States during the period from 1976 to 1988. In addition to summarizing the empirical findings, this report discusses the implications and limitations of these studies, and gives recommendations for improving mine safety. An annotated bibliography section appears in the appendix.

Jan 1, 2009

By T. A. Sullivan

The Bureau of Mines investigated modified sulfur concretes as one part of a program for utilizing sulfur in construction materials. The use of modified sulfur was studied as a means of preventing the stressing action in the concretes caused by the allotropic transformation of sulfur on solidification. Unmodified sulfur concretes have been prepared that have compression, flexural, and tensile strengths equivalent or better than Portland concretes. However, most of these concretes have been vulnerable to deterioration by weathering, temperature fluctuations, and freeze-thaw cycling. The sulfur was modified by reaction with dicyclopentadiene or dipentene before use as an aggregate binder. Sulfur concretes and modified sulfur concretes were pre-pared from acidic and basic type aggregates. Physical properties of the optimum mixtures were determined and compared with each other and with Portland cement concretes. The best results were obtained by reacting sulfur with 5 pct dicyclopentadiene to prepare modified sulfur concretes. Field testing of the concretes are in progress. Present results show that modified sulfur concretes are superior to unmodified sulfur concretes and equal or better than Portland concretes in compressive, flexural, and tensile strengths. Long-term aging characteristics of both modified and unmodified sulfur concretes are being determined.

Jan 1, 1976

By B. J. Moore

This publication contains analyses and related source data for 256 natural gas samples from wells and pipelines in 17 States. All of the samples were obtained and analyzed during calendar year 1977 as a part of Bureau of Mines investigations of the occurrences of helium in natural gases of countries with free market economies. This survey has been conducted in the United States by the Bureau of Mines since 1917. In late 1965, the survey was expanded to include foreign gasfields. The analyses published herein were made by mass spectrometer and a special helium analysis apparatus, which are described in Bureau of Mines Bulletins 4862 and 576.3 The results of the investigation of the occurrences of helium are published annually to make the information available as soon as possible to the gas industry and the public in general. Nineteen previous publications have presented the results of 11,317 gas analyses prior to 1977. The first three, Bulletins 486,4 576,5 and 617,6 contain analyses and related source data on 5,218 gas samples collected from 1917 through 1960. The other 16

Jan 1, 1978

By James L. Elder

The Bureau of Mines and the Alabama. Power Co. jointly conducted a first experiment in underground gasification of coal at Gorgas, Ala., during the fall and winter of 1946-47. This preliminary experiment showed that it was not difficult to maintain combustion of coal underground, and that coal in place could be completely gasified. It was noted that the high temperature developed by the gasification of coal in place brought about changes in overlying strata that appeared to be favorable to the process. The high temperatures caused the roof rock to become plastic, to expand, and to settle down on the mine floor directly behind the reacting coke face. These results were promising enough to warrant further investigation of the process. It was believed that if this action could be controlled properly with roofs of similar composition, it would tend to force the gas-making fluids underground against the coal faces. Plans for the second experiment were based in part on this favor-able roof action, and the successful operation of the planned initial straightline passages depended on this fact. Gorgas was chosen as the site for the second experiment for the following reasons: A tract of coal land of sufficient size was available and isolated from the main body of coal; the roof rock was similar in composition to that encountered in the first experiment; and the overlying strata were thick enough to eliminate some of the operating difficulties that had been encountered, In addition, power, water, and machine-shop facilities as well as an adequate supply of labor were available in this area, and the friendly cooperation of the Alabama Power Co. further recommended this site for the planned experiment.

Jan 1, 1951

By V. F. Parry

"INTRODUCTION During the war period the Bureau of Mines expanded its investigations on western coals principally in connection with Investigations of raw material resources for western steel production. Owing to the expansion of the steel industry, there was some concern regarding the availability of suitable coking coals; end because of the potential steel shortage, the production of sponge iron, using the lower-rank fuels, was considered. Work was conducted by the Bureau of Mines on exploration projects and on testing of coals both at the Central Experiment. Station at Pittsburgh, Pa., and at the Bureau of Mines Station at Golden, Cole.The results of these investigations are being published by the Bureau in several reports of investigations and technical papers. In making this resume of coal investigations, the work done by the Bureau of Mines at Pittsburgh in the Mining and Coal Carbonization Sections will be discussed and the investigations at Golden described in greater detail.INVESTIGATIONS OF WESTERN COALSThe Mining and Coal Carbonization Sections of the Coal Division, Bureau of Mines, under the supervision of A. L. Teeny es and J. D. Davis, respec¬tively, conducted many field investigations to locate and evaluate new sources of coking coals. Drilling explorations were made in Colorado, Wyoming, Utah, New Mexico, and Washington and revealed two important new reserves of coking coal. The first one studied was the Willow Creek bed at Kemmerer, Wyo., which was reported in 1945.3/ A recoverable reserve estimated at 11,200,000 tons was blocked out, and samples of coal were extracted for coking tests. The coking properties of the coal were not quite equal to those of Sunnyside coal, but it was indicated that a 50-percent blend of the Willow Creek with Lower Sunnyside will produce a satisfactory metallurgical coke based on Columbia steel standards."

Jan 1, 1948

By Jay W. Hawkins

Under an approved remining program, mine operators can remine abandoned coal mines without assuming legal responsibility for treatment of the previously degraded water, as long as the discharging waters are not further degraded and other regulatory requirements are satisfied. A U.S. Bureau of Mines review of 105 remining permits in Pennsylvania indicates that remining results in substantial reclamation of abandoned mine lands, utilization of significant quantities of coal, and reduction of contaminant loads (acidity and iron) from degraded mine drainage discharges. Normality tests performed on the water quality and flow data indicate generally nonnormal distributions and extreme right-skewness, tending toward lower values. The water quality of underground coal mines was observed to be more highly degraded in terms of acidity, iron, and sulfate than that of surface coal mines. The optimum baseline sampling scenario is 12 months in duration at a frequency of one sample per month. Analysis of water quality and flow rates before and after remining indicates that a majority of the mines exhibited either no change or a significant decrease in pollution rate because of remining. The discharge flow rate was the dominant controlling factor when the post-remining contaminant load was significantly better or worse than the baseline (pre-remining) load.

Jan 1, 2010

By Oliver Bowles

In 1943 the Bureau of Mines began a review of trends in consumption and prices of the more important nonmetallic minerals. The first report covering building materials4/ appeared in December of that year. The present paper, which deals with chemical raw materials and fertilizers, is the second of the series. The 34 years from 1910 to 1943, for which statistics are presented herein, comprise periods of uneventful peace, unparalleled prosperity, industrial depression almost to the point of stagnation, and two wars of world proportions.

Jan 1, 1945

By W. L. Cooley

The report provides a detailed analysis of 23 electrical accident countermeasures contemplated for use in the metal/non-metal mining industry. The costs and potential benefits of implementing groups of these countermeasures are estimated, and methods arc outlined by which the operator ran choose countermeasures in an effective manner. The analysis is based largely on an extensive electrical accident event tree which is developed in detail. For those countermeasures which are not currently technically feasible, several prototype devices were developed to help speed development. These included a trolley arc eliminator and a safer mine electricians multimeter.

Jan 1, 1982

By Joseph T. Singewald

The possible value of the red hematite iron ore of the southern Appalachian States, if some practicable method of concentrating it could be devised, has long been recognized. The ore is very low grade, and although in enormous quantities, particularly in the States of Alabama, Tennessee, and Georgia, is only at a few points rich enough to work, and even the best of it ranks among the lowest grade iron ores being mined in the United States. A cheap method of beneficiating this ore would make enormous quantities available and vastly increase the iron-ore resources of the country. However, this low-grade ore in effect constitutes a potential iron reserve, and as long as ample quantities of ore can be obtained elsewhere the question of its utilization does not demand immediate notice. Where these ores are in part of workable grade, however, a problem of more immediate importance arises which, from considerations of economy and prevention of waste in their mining, ought to be solved or, at least, attacked as quickly as possible. Where these ores are being worked they are usually intimately associated with lowergrade material that in mining is left behind. The difficulty and expense of going into ground broken by old workings makes the recovery of this lower-grade ore practically impossible and it is lost forever. Success in concentrating the red ores, therefore, would save material that is now being irretrievably lost. The successful largescale concentration of low-grade ore in the last few years on the Lake Superior iron ranges should encourage the attack of similar problems in the Birmingham district. While studying iron-mining methods in the United States for the Bureau of Mines, Dwight E. Woodbridge, consulting mining engineer of the bureau, was impressed with the importance of this problem, and believed it merited the attention of the bureau. Accordingly, Mr. Woodbridge had Mr. W. J. Penhallegon, general superintendent of ore mines and quarries of the Republic Iron & Steel Co., of Birmingham, send the author of this report five samples of the unworkable siliceous ores of the district. The results of concentration experiments with these ores made a more thorough 'and systematic investigation desirable. In consequence, the author subsequently collected samples in the district, and these became the basis of the experimental work described in this report. The results are published by the Bureau of Mines as a part of its efforts to increase efficiency in the utilization of mineral resources. The experiments were conducted in the geological laboratory of the Johns Hopkins University, Baltimore, Md., with the aid of Raymond Leibensperger, mining assistant. The chemical analyses were made by A. C. Fieldner, chemist, of the Bureau of Mines. The author wishes to express his appreciation of the courtesies extended to him by the mining companies of the district, and particularly to Mr. W. J. Penhallegon, of the Republic Iron & Steel Co. Thanks are also due Prof. W. B. Clark, director of the geological laboratory of the Johns Hopkins University, the unrestricted use of the facilities of the laboratory.

Jan 1, 1917

By W. M. Merritts

The control of coal dust created and released during the operation of continuous mining machines in bituminous-coal mines of the United States is a problem. The interest manifested in this problem indicates the seriousness of the hazards involved, particularly when the dust has not been abated at its source and has become air-borne. Officials of the Sunnyside No. 1 mine, Kaiser Steel Corp., were confronted with the problem of abating the coal dust created by operation of a recently installed continuous-mining machine, and they requested the aid of representatives of the Coal-Mine Inspection Branch, Bureau of Mines, United States Department of the Interior, in developing an effective method of allaying the coal dust at its source.

Jan 1, 1951

By James D. Brown

The Bureau of Mines has written a computer program in FORTRAN to facilitate the calculation of concentrations from X-ray intensities in electron probe microanalysis. Philibert's absorption and Castaing's secondary fluorescence corrections are used; no atomic number correction is included. Background and dead time corrections are applied to the data before calculating the relative intensities. Data from any type of electron probe microanalyzer can be used with the program.

Jan 1, 1965

By J. L. Eakin

The works and opinions of experts on well stimulation and related problems are summarized in this paper. The material is devoted to stimulative work in petroleum and natural-gas wells exclusive of the generally applied pressure maintenance and secondary-recovery methods. Its purpose is to review a collection of recent and available material on well-stimulation methods and techniques. Each separate discussion is accompanied by a selected bibliography. An author index is included.

Jan 1, 1964

By J. L. Eakin

The works and opinions of experts on well stimulation and related problems are summarized in this paper. The material is devoted to stimulative work in petroleum and natural-gas wells exclusive of the generally applied pressure maintenance and secondary-recovery methods. Its purpose is to review a collection of recent and available material on well-stimulation methods and techniques. Each separate discussion is accompanied by a selected bibliography. An author index is included.

Jan 1, 1964

By Wilbert J. Huff

The organization of the Explosives Division is indicated by the accompanying chart (fig. 1). As this has been discussed in a previous report3/, it will not be considered further in this report. The activities of the various units are outlined below. I. INFLAMMABILITY OF GASES AND VAPORS4/ Determination of the Explosion Hazards of Combustible Gases and Vapors Found in Mines and Industries The Explosives Division maintains, at the Pittsburgh Experiment Station, a laboratory specially equipped for the determination of the explosion hazards of combustible gases and vapors. Of particular importance, is the determination of the chemical composition within which explosions may occur and beyond which there is no danger of explosion, combustion or inflammation. These limits, known as the limits of inflammability, as determined by this and other laboratories, have been compiled in Bulletin 279 of this Bureau. The last revised edition (1931) of this bulletin has been exhausted. Since it was published, the Pittsburgh laboratory has determined the limits of about 40 combustibles and has ascertained more precisely ant accurately many previously published limits.

Jan 1, 1938

By W. J. Wenger

THIRTY-FOUR analyses of crude oils from the fields of the Four Corners Area of Arizona, Colorado, New Mexico, and Utah are presented and compared. The samples, taken from formations in four geological time periods, have high gravity and low-sulfur, -nitrogen, and -asphalt content. Generally, the oils are paraffinic in the low-boiling fractions, with increasing naphthenicity in the higher-boiling fractions. Oils from Cretaceous formations resemble other Cretaceous oils in the Rocky Mountains, but oils from Permian and Pennsylvania formations are unlike other oils of these ages in the Rooky Mountains. The differences in the oils are minor and cannot be used to distinguish between fields or between producing formations. With minimum special processing, the oils should yield large amounts of good-quality motor fuels. INTRODUCTION The only place in the United States where four States have a common junction is known as the Four Corners Area. This area (fig. 1) includes the northeast corner of Arizona, the southwest corner of Colorado, the northwest corner of New Mexico, and the southeast corner of Utah. It includes three major geological basins: The Black Mesa, the San Juan, and the Paradox. Major oil developments have occurred in both the San Juan and Paradox basins, but no discovery of commercial importance has been made in the Black Mesa basin.

Jan 1, 1960